CN101896643A - The Nano tube array of titanium dioxide of high-sequential - Google Patents
The Nano tube array of titanium dioxide of high-sequential Download PDFInfo
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- CN101896643A CN101896643A CN2008801082266A CN200880108226A CN101896643A CN 101896643 A CN101896643 A CN 101896643A CN 2008801082266 A CN2008801082266 A CN 2008801082266A CN 200880108226 A CN200880108226 A CN 200880108226A CN 101896643 A CN101896643 A CN 101896643A
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- 239000002071 nanotube Substances 0.000 title claims abstract description 162
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000004408 titanium dioxide Substances 0.000 title claims description 17
- 238000007743 anodising Methods 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 92
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 29
- 230000012010 growth Effects 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 13
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims description 12
- 239000005486 organic electrolyte Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
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- 230000015572 biosynthetic process Effects 0.000 claims description 9
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 230000002045 lasting effect Effects 0.000 claims description 6
- -1 methane amide Chemical class 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
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- 230000002194 synthesizing effect Effects 0.000 claims 3
- 210000004027 cell Anatomy 0.000 claims 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 24
- 239000011888 foil Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 77
- 230000008901 benefit Effects 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 15
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 15
- 229960005196 titanium dioxide Drugs 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
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- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
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- 239000000463 material Substances 0.000 description 7
- 206010070834 Sensitisation Diseases 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
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- 230000008313 sensitization Effects 0.000 description 6
- 238000000352 supercritical drying Methods 0.000 description 6
- 230000003321 amplification Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- AZHSSKPUVBVXLK-UHFFFAOYSA-N ethane-1,1-diol Chemical compound CC(O)O AZHSSKPUVBVXLK-UHFFFAOYSA-N 0.000 description 4
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
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- 238000003801 milling Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910001029 Hf alloy Inorganic materials 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004830 Super Glue Substances 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910004353 Ti-Cu Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000002800 charge carrier Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
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- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Disclosing length, to surpass 10 μ m and aspect ratio be 10,000 the making from the titania nanotube array of directed airtight assembling, and its method comprises the permanent electromotive force anodizing of titanium.Also disclose the condition that realizes complete anodizing of Ti foil sample and absolute customizability, obtained mechanically surpassing reliably the titanium oxide self-support film of 1000 μ m.
Description
The cross reference of related application
The application requires to enjoy the 60/952nd, 116, No. 119 right of priority based on 35 U.S.C. § 119 of provisional application of submitting on July 26th, 2007, and the full content of this application is combined in this by reference.
The relevant subsidy
The present invention develops under the government-funded of the special funding DE-FG02-06ER15772 of Ministry of Energy.Government has certain right in the present invention.
Technical field
The present invention relates to the high-sequential TiO of length
2The preparation of nano-tube array, relating more specifically to array length is that 10 μ m are to vertical orientated titanium oxide (titaniumoxide) nano-tube array that surpasses 1000 μ m.
Background technology
That anodizing by Ti thin slice or sheet is made is vertical orientated, the TiO of high-sequential
2Nano-tube array becomes more and more important owing to its outstanding performance in various application becomes, and described application comprises dye sensitization solar battery [1-4], water photoelectrolysis hydrogen manufacturing [5-9], photochemical catalysis [10-13], gas sensor [14-19] and living species [26] application.Because above-mentioned application and geometrical surface are closely related, therefore must pay close attention to overlength TiO specially
2Synthesizing of nano-tube array.
Summary of the invention
Two basic norms judging the nano-tube array growth are lasting oxidation and hole growths of metal, it depends on the chemistry/field assist in dissolving [15 of formed oxide compound, 16,22] and by the nanotube length that running balance determined between process of growth and the dissolution process.As a result of and the part of this discovery, the two-sided anodizing of titanium foil sample in multiple ionogen produced the nano-tube array [20,21] by the thin separated length of barrier layer.By the anodizing in various ionogen, hewed out and realized the synthetic of nano-tube array, pass through the anodizing of Ti paper tinsel now, it is the synthetic method of the nano-tube array of assembling from directed six sides of 10 μ m～surpass, 1000 μ m that length is provided, and has produced further purpose of the present invention, feature or advantage.
Further purpose of the present invention, feature or advantage provide and contain the non-aqueous solution system that the polarity organic electrolyte is enough to oxidation as electrolytic medium, ionic concn and makes the hole growth, and wherein the thickness of porous oxide is the function of titanium foil thickness.
Another object of the present invention, feature or advantage are the anodizing by metal, material or its alloy of titanium, nickel, hafnium, tantalum and any other suitable valve metal and so on, and 10 microns synthetic methods that reach the nano-tube array of longer self-orientating high-sequential are provided.
Further purpose of the present invention, feature or advantage are the absolute customizabilities (tailorability) that method is provided when obtaining the nanotube of the required/length that requires.
Further purpose of the present invention, feature or advantage are that the form with free-standing (self-standing) film provides the synthetic of nano-tube array.
Another object of the present invention, feature or advantage provide a kind of negative electrode, and described negative electrode is made by metal or any other suitable metal, material or its alloy of platinum, nickel, palladium, copper, iron, tungsten, cobalt, chromium, tin and so on.
Another object of the present invention, feature or advantage provide anodized at various temperatures nano-tube array, have the nanotube of the geometrical shape of variation with acquisition.
Further purpose of the present invention, feature or advantage provide aperture flat and/or columniform big area TiO uniformly
2The preparation of film of Nano tube array and application can be used as solar energy collector or solar cell.
Further purpose of the present invention, feature or advantage provide the DSSC film of improvement, and described film can provide electron path efficiently, have high surface-area, and can grow into the length that can cause light conversion efficiency to surpass silica-based solar cell.
Another object of the present invention, feature or advantage provide flat and columniform, the uniform big area TiO in aperture
2The preparation of film of Nano tube array and application are applicable to the filtering biological species.
Further purpose of the present invention, feature or advantage provide multiple anodizing parameter control, change the connectivity of tube and tube, thereby change the packing density of nanotube in the array.
Another object of the present invention, feature or advantage provide the method for accurate control nano-pipe array thin film structural performance, comprise the size of controlling single nanotube, as the connection and the degree of crystallinity of aperture, wall thickness, length, tube and tube.
Another object of the present invention, feature or advantage provide a kind of method, use ultrasonic agitation and other suitable method in the method, separatory membrane from any metal remained substrate.
Can form the method for vertical orientated Nano tube array of titanium dioxide by using electrochemical oxidation, realize one or more aforementioned purposes, feature or advantage.This method comprises provides the two electrodes that contains working electrode and counter electrode structure, anodizing working electrode in ionogen, described ionogen has been optimized to and can have kept running balance between process of growth and dissolution process, promote the growth of nano-tube array to promote the hole growth by the lasting chemical oxidation that working electrode is provided by dissolving formed oxide compound.In a preferred form, working electrode is a titanium foil, and counter electrode is a platinum, and ionogen is for containing NH
4F and H
2The ethylene glycol of O, the oxide compound of formation are titanium oxide.
Can form the method for nano-tube array by using electrochemical oxidation, realize another one or a plurality of aforementioned purpose, feature or advantage.This method comprises providing and contains as the titanium foil of working electrode with as the two electrodes structure of the platinum foil of counter electrode, the anodizing titanium foil forms titanium dioxide in electrolyte solution, and described electrolyte solution comprises the NH of certainweight percentage ratio (wt%) in ethylene glycol solution
4F and H
2O, dissolving titanium dioxide forms the nano-tube array of the long-range order that shows tight assembling and high aspect ratio, this nano-tube array grows to the given optimum length of working electrode thickness by the lasting oxidation and the hole of titanium foil, by NH in control anodizing voltage, anodizing time and the ethylene glycol solution
4F and H
2The weight percentage of O keeps running balance between process of growth and dissolution process.
Can realize one or more aforementioned purposes, feature and/or advantage in addition by nano-tube array.This nano-tube array comprises a plurality of titania nanotubes from directed vertical orientated length at least 10 μ m.A plurality of certainly directed vertical orientated titania nanotubes are formed by electrochemical oxidation.
By the following description book and claim, aforementioned purpose of the present invention, feature and/or other advantage will become apparent.With reference to accompanying drawing, these accompanying drawings have formed the part of this specification sheets in specification sheets, and have shown by diagram and indefiniteness ground therein and can implement specific form of the present invention.These embodiments are not represented four corner of the present invention, but the present invention can be used for multiple other embodiment, has also explained protection scope of the present invention in this manual with reference to claim.
Description of drawings
Fig. 1 has shown at NH
4NH when F concentration is given regularly for the acquisition maximum growth rate
4The wt% of F and H
2The ratio (black line) of the vol% of O.This figure also shows NH
4The wt% scope of F wherein according to an aspect of the present invention, is given periodic water, the complete anodizing of all thickness Ti paper tinsel that is produced for concentration.
Fig. 2 a shown according to an exemplary aspect of the present invention, the FESEM image of the complete anodized Ti foil sample first half (the black line mark of seeing towards Fig. 2 a bottom the separation between two nano-tube arrays shown in Fig. 3).
Fig. 2 b shows the section FESEM image of the fracture sample of nano-tube array of the present invention.
Fig. 3 has shown the first half of free-standing titanium dioxide film of the present invention and the FESEM image of Lower Half.
Fig. 4 a has shown the TEM image of an exemplary aspect according to the present invention crystalline nanotube in the time of 580 ℃.
Fig. 4 b has shown the diffraction pattern of selecting the district, and it has shown the anatase octahedrite phase of nano-tube array according to an aspect of the present invention.
Fig. 5 a has shown the FESEM image of the low power amplification of the nano-tube array that forms circulation film (flow-through membrane) according to an exemplary aspect of the present invention, through chemical milling.
Fig. 5 b has shown the FESEM image that the high power of the partially-etched barrier layer of nano-tube array of the present invention is amplified.
Fig. 5 c has shown the FESEM image that the high power of bottom of the nano-tube array of complete opening of the present invention is amplified.
Fig. 5 d has shown the FESEM image that the high power at top of the nano-tube array of complete opening of the present invention is amplified.
Fig. 6 a has shown another FESEM image according to the nano-tube array of one aspect of the invention that contains illustration, and described illustration has shown the high magnification map picture of this nano-tube array.
Fig. 6 b has shown the FESEM image in the nanotube films cross section that contains illustration, and described illustration has shown the high magnification map picture of this nanotube films.
Fig. 6 c has shown the high power amplification FESEM cross-sectional image of the mechanical breaking sample of nano-tube array of the present invention.
Fig. 7 a has shown the high power amplification FESEM image at the back side (barrier layer) of the nano-tube array of having made according to one aspect of the invention.
Fig. 7 b has shown the high power amplification FESEM image at the partially-etched back side (barrier layer) of the nano-tube array that has made.
Fig. 7 c has shown the high power amplification FESEM image of the complete etched back (barrier layer) of the nano-tube array that has made.
Fig. 8 has shown that an exemplary aspect according to the present invention faces the FESEM image of the nano wire that forms once in a while when boundary's point is dry on the surface of free-standing titania nanotube/porous-film.
Fig. 9 a has shown the digital picture according to the Nano tube array of titanium dioxide of an exemplary aspect of the present invention (as anodized) on titanium foil.
Fig. 9 b shown separate with titanium foil and the barrier layer etching after be kept at the digital picture of the flat film in the ethanol alcohol.
Fig. 9 c has shown the directly digital picture of taking-up and exsiccant film from water/ethanol.
Fig. 9 d has shown the digital picture of the flat film that obtains according to an aspect of the present invention behind critical point drying.
Figure 10 has shown the GAXRD pattern of the annealing nano-tube array sample that shows the anatase octahedrite peak value according to an aspect of the present invention.
Figure 11 has shown an exemplary aspect according to the present invention TiO free-standing, mechanically reliability and durability after annealing
2The FESEM image that the high power on the surface of film is amplified.
Figure 12 has shown the cylindric TiO that makes according to an exemplary aspect of the present invention, the anodizing of external diameter section by Ti tubulation (tubing)
2The aerial digital picture of nano-pore membrane.
Figure 13 for example understands the solar cell that uses Nano tube array of titanium dioxide of the present invention.
Figure 14 is to use TiO of the present invention
2The synoptic diagram of the biofiltration experimental installation of film.
Figure 15 has shown that glucose passes through according to the time dependent scatter diagram of the titanium dioxide film of an exemplary aspect of the present invention.
Embodiment
The metal oxide semiconductor nanotube of making the length of high-sequential, high aspect ratio is the key that improves various performances based on device nanotube or that transform and technology.In this manual, provide simple and reliable chemical anode making route, can be used for realizing high aspect ratio and length be the vertical orientated TiO of the super large surface-area of at least 10 μ m
2Nanotube.The film of the overlength nano-tube array that these class both sides are opened wide has formed the structure of new generation of the catalytic film that can be used in biofiltration, solar cell, implant and the fuel cell.No matter nano-tube array is flat or columned, all has big area and hole dimension uniformly; Therefore, nano-tube array height of the present invention is applicable to any above application, even can further consider that all can be from TiO of the present invention
2The characteristic that nanotube shows and benefited technical field.Because the present invention has demonstrated the ability that array is separated into single nanotube, it means the electric assemble nanometer pipe array that might realize being used for multiple other application.
TiO by the anodizing making
2Nano-tube array has constituted vertical orientated self-organizing structures.Array vertical orientated is ideal very in such as dye sensitization solar battery and light-catalysed many application.Under the situation of dye sensitization solar battery, vertical orientated stop electron recombination and be convenient to electronics flow to contact surface, for photochemical catalysis such as photolysis, the vertical orientated hydrogen of being convenient to moves from single pipe.TiO
2Nanotube has many special advantages.Advantage is not reduce by how much and structurally ordered degree just can increase effective internal surface area.Second advantage is by the geometric parameter of precision design and control texture, just can influence absorption and propagation by the light of described structure.Another key advantages is that directed porosity rate, degree of crystallinity and the directional properties of nano-tube array makes it become the attractive electronics leak path of vector charge transfer between the interface.For the application of integrated vertical orientated titania nanotube, these advantages are from existing TiO
2Manifested in the unusual enhancing of performance.
The present invention seeks that field of enhanced is dye sensitization solar battery (DSSC) by the high aspect ratio nano pipe array of integrated high-sequential.At present, relatively poor based on the efficient of the DSSC of crystallization nano particle metal oxide semiconductor film, reason is its absorption difference to lower energy photon in ruddiness and near infrared light.Use thicker nanocrystal film to be offset by the low-velocity electron diffusion by random network of nanoparticles.In the unidimensional structure, because there is the additional surface that is enclosed in the hollow structure the inside long-pending, nano-tube array has higher geometrical surface.The most important geometric parameter of nano tube structure is the nanotube length of aperture, wall thickness and the representative nano-tube array thickness of vertical orientated growth on substrate.For given aperture and wall thickness, internal surface area almost increases with nanotube length linearly.
Up to the present, TiO of last generation
2Nano-tube array can not grow into enough length, is difficult to bring into play the effect of the higher geometrical surface relevant with array.Further improve array length and require to improve Ti-TiO
2The interface is the field auxiliary rate (field-assisted rate) when mobile in the Ti metal.Prima facie improves an auxiliary Ti-TiO
2Ratio as if can guarantee to strengthen electric field, yet big electric field can produce thicker barrier layer, hinders Ti
4+Ion is outwards carried from titanium-base, and OH
-And O
2-Ion is inwardly carried.In addition, in containing the water-soluble ionogen of high concentration ion, TiO
2Barrier layer can experience dielectric breakdown when exceeding electric field threshold value.Behind the dielectric breakdown, electronic conduction rather than desired ionic conduction have been contributed most anodizing electric current.By reducing electrolytical water-content to being lower than 5%, can make barrier layer thinner or quality is lower, strengthen ion thus and carry, the present invention just can alleviate these influences like this.In addition, it is wideer that the disruptive potential that oxide compound is higher in the nonaqueous electrolyte can make the scope of the anodizing current potential when taking place to form nanotube.For example, methane amide and N-methylformamide are the height polar, and specific inductivity is respectively 111 and 182.4, the specific inductivity of the water much larger than 78.39.For given current potential, higher electrolyte capacitance amount can be induced on zone of oxidation and be formed more electric charge, improves TiO
4+Ionic extracts, and higher ionogen (electrolute) polarity will make hydrofluoric acid (HF) be easy to dissolving, improve it at TiO
2-The property obtained at electrolyte interface place.Under the situation of organic electrolyte, with the water ratio, the supply of oxygen is more difficult, has therefore reduced the trend that forms oxide compound.Simultaneously, water-content reduces the chemical dissolution that has reduced oxide compound in the fluorine-containing ionogen, therefore helps the formation of longer nanotube.
Method
Therefore, obtain as an example and in test, below describe the method that realizes the nanotube maximum growth.According to an exemplary aspect of the present invention, the titanium foil of all thickness, for example 0.25,0.5,1.0 and the thick sample of 2.0mm, before anodizing,, wash with Virahol then with the acetone cleaning.Although quoted concrete thickness, should be appreciated that described paper tinsel can be to be easy to anodized any thickness.The present invention is understood that the thickness of the oxide compound that forms is the function of working electrode thickness, for example the thickness of titanium foil/film.Titanium foil of the present invention has constituted " thick film ", such as the technician usually understanding and knowing.Titanium foil has enough thickness, can provide to be convenient to handle and to promote anodized enough big rigidity and stability.Titanium foil is high level titanium.The present invention is not limited only to pure titanium foil (as 99.99% purity; Alfa Aesar, Ward Hill, anodizing MA).For example, anodization process of the present invention still can be operated in the paper tinsel of impurity is arranged, and for example, contains the paper tinsel of 40～50%Ti.In another aspect of this invention, to the substrate of substrate, just can provide titanium-iron (Te-Fe) and titanium-copper (Ti-Cu) film by two kinds of materials below the cosputtering as conduction.
Anodizing can with titanium foil as working electrode, platinum foil two electrodes structure as counter electrode in, under about 22 ℃ of room temperature, carry out with constant potential.Although anodizing is at room temperature carried out, should be appreciated that anodizing can carry out at various temperatures.For example, anodizing can be from-5 ℃ to 100 ℃ or be easy to carry out in anodized any other temperature range, to form the nano-tube array of the present invention of various geometrical shapies and form.Use the anode electrolytic cell titanium foil, self-orientating, six sides synthetic method assembling, the free-standing nano-tube array that can provide length to surpass 10 μ m, described nano-tube array is as 10 μ m～above the nano-tube array of any length of 1000 μ m.The technician will be understood that Nano tube array of titanium dioxide of the present invention can have alternative assembling to arrange to substitute preferred six side's arrangement modes.Yet, to compare with thinkable other assembling arrangement, six side's arrangements can provide superior array structure integrity, and the gap between the adjacent tubes in the energy optimal seal nano-tube array.Gap in the restriction array between the adjacent tubes can be limited and be entered undesirable material, and can limit flaw and enter in the array.It will be appreciated by those skilled in the art that ionogen can be for example based on the aqueous electrolyte liquid of acid amides, or nonaqueous electrolyte, as the polarity organic electrolyte.The volt ohm-milliammeter that computerizeds control can write down the anodizing electric current with time correlation, and anodized sample carries out ultrasonic clean in deionized water, to remove surface debris.Can use the form of field-emission scanning electron microscope (FESEM) research anodizing sample.
As putting down in writing in this manual, ethylene glycol (EG) shows the growth velocity of titania nanotube extremely fast [20] up to 15 μ m/min as solvent in electrochemical oxidation, this almost is five times that nanotube forms maximum rate [9] in based on the ionogen of acid amides, and has surpassed the order of magnitude that is higher than growth velocity in the aqueous solution [16].The nanotube that forms in EG shows the long-range order that closely manifests in the assembling six sides and very high aspect ratio (～6000).Higher aspect ratio all is beneficial in many application.Especially, high aspect ratio helps the vector charge transport in the solar cell application of using Nano tube array of titanium dioxide of the present invention.Also find at utmost to reduce among the EG lateral etch of nano-tube array.Equally, this nano-tube array show uniform wall thickness and the hole thick, this is different from anodized anodized nanotube in other aqueous electrolyte, other aqueous electrolyte is because the top of pipe upwards forms (top-up formation) (promptly, the top of nanotube is longer than the time of bottom in electrolyte solution, therefore the solvency action that is exposed in the ionogen is more permanent), this ionogen can dissolve the wall and the hole of pipe more at the top of sample than the bottom.In an example, in order to control this solubilizing reaction, by water-content being limited to the level that contains water contained in the HF solution, thereby reduce the H+ ionic concn.This water can guarantee the Ti paper tinsel at the field of bottom, hole assisted etch, and in addition, protophilic DMSO accepts the proton from HF, thereby has reduced its activity.This can make the DMSO nanotube in depth grow in the titanium foil, and does not have any significantly sacrificing from the aperture.Exist DMSO can improve space charged region in the hole, therefore avoided lateral etch, can cause the stable hole growth and the low chemical milling of nanotube walls.For example, in an exemplary aspect of the present invention, use the NH that contains sufficient wt%
4F and H
2The EG ionogen of O obtains nano-tube array when anodizing, during it is presented at the porosity of deduction structure and nano tube structure and forms behind the dissolved titanium dioxide, and TiO
2Formation efficient near 100%, this shows does not have side reaction during anodization process, and formed TiO
2The body chemical dissolution of nano-tube array can be ignored.The repeated use of solution shows after the anodizing, and the growth of the passive metal oxide compound of hundreds of nanometer (passive oxide) does not form nanotube, and this is only adding NH
4Just can be recovered when F and ethylene glycol.This finds strong explanation, the consumption explanation of H+ in the used solution and F-species, and it can not produce enough local acidifyings in the bottom, hole and limit barrier layer thickness.Therefore, be not subjected in the organic electrolyte of oxide compound in fluoride in (non-thickness limited) growth of thickness limits, the length of nano-tube array is limited by retrievable fluorochemical and hydroxide ion.Electrolytical ionic concn is not unique anodizing variable.Anodized other significant variable comprises for example voltage, anodizing time, water-content and previously used ionogen.All these anodizing variablees can make up, to obtain to be easy to realize the nano-tube array of the length and the form of various discrete application.Therefore, only be subjected to the longer nanotube of acquisition of the complete anodizing restriction of initial Ti paper tinsel, its challenge part is to obtain optimum growh speed by other anodizing variable of controlling electrolytical composition and time length and above introducing at least and describe in detail in application specification.
Though EG is easy to electrochemical oxidation to heavens, should be appreciated that, the invention is not restricted to only use the ionogen that contains EG, the present invention's expection can be used other polarity organic electrolyte, for example is used to provide methane amide (FA), methyl-sulphoxide (DMSO), dimethyl formamide (DMF) and the N-methylformamide (NMF) of fluoride ion.The present invention can use the DMSO ionogen that contains following component to prepare vertical orientated TiO in another exemplary aspect expection
2Nano-tube array [23]: hydrofluoric acid (HF), Potassium monofluoride (KF) or Neutral ammonium fluoride (NH
4F).The technician is appreciated that the chemical of this class such as HF has surrogate.Use contains competent fluoride ion such as NH
4The ionogen of F can provide enough TiO
2Etching.For example, with the ionogen that contains 2%HF among the DMSO, 70 hours time length, use the anodizing current potential of 60V, can realize that for 3,475 the geometric area that calculates length surpasses the nanotube of 101 μ m, internal diameter 150nm, wall thickness 15nm.The weak bounding force of nanotube that DMSO makes and following oxide barrier layers and the low bounding force between the tube and tube will help its separation for the application that requires the dispersive nano-tube array.
For the ethylene glycol ionogen, when 60V, can be observed the highest nanotube growth speed [20].Also to the Ti paper tinsel of all thickness, the Ti paper tinsel thick as 0.25～2.0mm contains different N H in EG
4F and H
2Under 60V, carry out anodizing research in the ionogen of O concentration.Be for different NH shown in Fig. 1
4F concentration, the optimum concn of the water that is satisfied when realizing the highest growth rate.At given NH
4F and H
2In the concentration range of O, because NH
4The wt% of F increases the anode dissolution that is produced can pass through H
2The increase of O concentration is compensated, and produces higher growth velocity, therefore obtains longer nanotube length.For instance, Fig. 1 has also shown H
2O and NH
4The F range of concentrations can realize the complete anodizing (utilization) of 0.25mm and 0.5mm Ti foil sample in this scope, as described in the following embodiments, described embodiment is in fact the example of various electrolyte compositions.
Embodiment 1: in an exemplary features of the present invention, with the NH of 0.1wt%～0.5wt%
4F, 2% water carry out complete anodizing to the foil sample of 0.25mm, cross over the nano-tube array that thin barrier layer has obtained two 320～360 μ m.
Embodiment 2: in another exemplary features of the present invention, use the NH that in EG, contains 0.3wt%
4F and 2%H
2The solution of O 96 hours obtains nano-tube array.The titanium foil 168 hours (7 days) of anodizing 0.5mm in identical ionogen, the maximum ga(u)ge that obtains is～380 μ m, this shows that the active electrolyte species have obtained utilizing fully.
Embodiment 3: in another exemplary features of the present invention, in EG, contain 0.4～0.6%NH
4F and 2.5%H
2Realize the complete anodizing (referring to Fig. 1) of 0.5mm paper tinsel in the ionogen of O; The nano-tube array length that obtains on the oxidase substrate both sides is found to be 538 μ m.This 538 μ m is by at 0.4wt%NH
4What the titanium foil of complete anodizing 0.5mm was realized in 168 hours under 60V among the EG of F and 2.5% water.
Embodiment 4: in another exemplary aspect of the present invention, containing 0.5wt%NH
4The Ti paper tinsel that anodizing 2.0mm is thick under 60V among the EG of F and 3.0% water 216 hours (9 days) has obtained the nano-tube array (referring to Fig. 2 a and 2b) of length above 1000 μ m.Form the free-standing nano-tube array that thickness surpasses 2mm simultaneously at anodized paper tinsel on the both sides, base portion plane (black line of seeing towards Fig. 2 a bottom indicates the separation between two nano-tube arrays or the base portion plane), as shown in Figure 3.This anodized structure in the oxygen environment under 580 ℃ with 1 ℃/minute rate of temperature fall annealing 3 hours.It is anatase octahedrite that the analyses of grazing angle X-ray diffraction (GAXRD) and transmission electron microscopy (TEM) are disclosed this nanotube.Fig. 4 a has shown the TEM image of crystallization nanotube, the diffraction pattern alleged occurrence anatase octahedrite shown in Fig. 4 b, and this is a kind of titanium dioxide TiO of natural appearance
2Crystalline form.
Nano-tube array one end of having made opens wide, relative end sealing; A relative end is the place that forms pipe by the titanium foil galvanic corrosion.In an exemplary aspect of the present invention, the water mixture of 2.0% HF can be used for handling the closed side several minutes of this self-support film, to remove tamper.Fig. 5 a～d has shown a plurality of images of back side etch sample.Particularly, Fig. 5 a has shown the local opening of etching after 1 minute, and Fig. 5 b has shown the complete opening of etching after 2 minutes, and Fig. 5 c has shown the array bottom of opening wide fully, and Fig. 5 d has shown the top surface of anodized nano-tube array sample.
Also carried out the surface-area measurement.In one aspect of the invention, with exsiccant TiO
2Film of Nano tube array is evacuated down to the pressure of 2mm Hg, measures the physical adsorption amount of nitrogen under 77.35K.Record gas adsorption volume (cc/g@STP) is to the adsorption isothermal curve of relative pressure.Use BET (Brunauer, Emmett and Teller) equation to obtain on sample surfaces, forming the needed gas volume of individual layer.Long-pending from the known size and the quantity calculating real surface of adsorption gas molecule.Following table 1 has shown surface-area and pore volume (40V, the inner aperture of 70nm, 12 μ m length, 0.3% NH of the sample in different inner apertures
4F and 2% H
2O, 6 hours; 60V, 18 μ m length, 0.3%NH
4F, 2% H
2O, 6 hours).
Can infer that from table 1 surface-area is relevant with aperture/volume.The BET surface-area is measured and is shown that for the nano-tube array of 70nm and 105nm internal diameter, average surface area is respectively 38m
2/ g and 36m
2/ g.
More than shown the TiO that surpasses 1000 μ m by anodizing synthetic length
2Nano-tube array, the thickness of self-support film surpasses 2mm.The original depth that depends on the Ti foil sample can change the bath condition, for example NH in the ethylene glycol
4F and H
2The wt% concentration of O is to realize the complete anodizing of foil sample.As above affirmation, the present invention understands, and further changes batch condition, just can provide even the foil sample of bigger thickness such as the complete anodizing of Ti, as the thick 2.0mm that reaches.Therefore, by keeping electrochemical oxidation, electrochemical dissolution and the controlled anodizing of chemical dissolution process equilibrated, the nanoporous of the length that the present invention did not reach before can providing and having and the anodizing formation method of nano tube structure.In addition,, just can control the structural performance of nano-tube array, comprise the dimension of single nanotube, as aperture, wall thickness, length, tube and tube connectivity and degree of crystallinity by keeping the running balance between process of growth and the dissolution process.It is considered herein that titanium foil can be near 100% to the transformation efficiency of titanium oxide by keeping the running balance between process of growth and the dissolution process.
Embodiment 5: in another exemplary characteristics of the present invention, use the titanium foil of all thickness, make flat array film, to be used for discrete application, filtering biological species [26] for example.Preparation Ti paper tinsel is used for anodizing, and this can comprise one or more following steps: with the Micro-90 solution ultrasonic cleaning of dilution, drip washing and dry in nitrogen in deionized water and ethanol.In order to make flat array film, can make the electrolyte composition that contains 0.3wt% Neutral ammonium fluoride and 2vol.% water in the spent glycol.At room temperature (～22 ℃) carry out anodizing with the platinum foil negative electrode.Can use direct supply to be used as voltage source, drive anodizing process.The electric current that can use volt ohm-milliammeter to measure.Under 60V, carry out anodizing in lasting 72 hours, can obtain the nanotube length (aperture 125nm, standard deviation 10nm) of about 220 μ m.Will be anodized sample immerses in the ethanol alcohol and carries out ultrasonic agitation, separates with following Ti substrate up to film of Nano tube array.The stress at barrier layer-metal interface place is convenient to it and is broken away from from substrate.It will be appreciated by those skilled in the art that also to have other means that nano-tube array is broken away from from substrate, for example, impact anodized sample by voltage pulse, or only with substrate mechanical or manually disengaging from nano-tube array.Fig. 6 a and 6b have shown the FESEM image of the various enlargement ratios in film upper surface and cross section, and Fig. 6 c has then shown the cross-sectional image of sample mechanical breaking.Fig. 7 a has shown the back side of the nano-pipe array thin film that has made, i.e. barrier layer one side.Because nano-tube array forms from blind end by the titanium foil galvanic corrosion, this just requires to open blind end; In one aspect of the invention, use barrier layer one side of the hydrofluoric acid/sulphuric acid soln coated film of dilution,, finish thus and open blind end with etching oxide.Clean oxide compound with ethanol alcohol then.Fig. 7 b has shown the back side of partly opening wide.Repeat pickling, unlimited fully up to the hole, seen in Fig. 7 c, the ultrasonic cleaning film is removed any chip relevant with etching then.Remove liquid and behind air drying, (originally being flat) film obviously curls (referring to Fig. 9 c), makes it be not suitable for filtration application.Therefore this kind performance uses the liquid of low surface tension to clean film, as hexamethyldisilazane (HMDS) mainly due to the surface tension that acts on the film.Even now can alleviate this problem to a certain degree, but real breakthrough is to use the method that is called critical point drying to remove solution from film.In critical evaporator, can keep the planeness of film when dry with carbonic acid gas, as best illustrated among Fig. 9 d.Behind the critical point drying, the surface of film can manifest nanofiber surface (referring to Fig. 8) once in a while, and this can remove by film is carried out ultrasonic agitation.Fig. 9 a～d is with below the figure explanation: Fig. 9 a has shown anodizing and has cleaned the thick nano-pipe array thin film of 200 μ m on the titanium foil substrate of back; Fig. 9 b has shown by ultrasonic agitation and has separated with following Ti substrate and remove after the barrier layer by chemical milling, has been immersed in the film in the ethanol alcohol; Fig. 9 c show directly from solution, take out, exsiccant film (noting curling on a large scale) then; Fig. 9 d shows the flat film that obtains behind the critical point drying.Should be pointed out that the film that can make area～2.5cmx5cm, wherein the upper limit of size can be passed through CO
2The ability decision of critical point drying instrument; In any case this method can adapt at an easy rate makes the larger area film.Find that the thick or thicker film of 40 μ m is enough firm for handling easily.For example, can make free-standing that minimum thickness is 4.4 μ m but quite crisp film.The film of the present invention that gained has been made has unformed structure.Be that degree of crystallinity relates to for any that electric charge carrier produces and the application of conveying/migration is very important, is included in the photoelectrolysis of photochemical catalysis cleaning, water and the application of solar cell [6,28,25].Therefore, film is by the low-temperature annealing crystallization, to prevent to destroy the planeness of film.Annealed 1 hour down for 280 ℃ in oxygen atmosphere, film is easy to crystallize into the anatase octahedrite phase, referring to Figure 10; Use diffractometer record GAXRD pattern.The surface of the described film in annealing back is seen shown in Figure 11.
Figure 12 has shown the cylindric TiO that the complete anodizing of the Ti tubulation (tubing) of hollow is made
2Film of Nano tube array.Be similar to its flat film analogue, during by critical point drying method drying, the best when columned film begins, and can pass through low temperature annealing crystallization.
Use
Benefiting from an application of the present invention, as mentioned above, can be sun power.Sun power is a kind of cleaning and the reproducible energy, also promptly almost can obtain everywhere on earth.Yet it is not feasible energy derive for many application, because compare with the existing energy, the cost height of its per unit energy must form obstacle.The prime cost of traditional solar cell is the semi-conductive cost that is used to produce battery, normally silicon.Silicon must be high purification, and process for purification is energy-intensive, and this has caused the expensive of final product.For the available device of best commercial sources, the light conversion efficiency of silicon solar cell (total energy that battery produces and the ratio of the total sun power that is exposed to battery) is 14～16%, so its production is very expensive.There are some factors to influence the light conversion efficiency of solar cell, comprise the electron amount of generation and the speed of electron recombination.Therefore, the invention provides improved dye sensitization solar battery (DSSC) film, this film can provide electron channel efficiently, has high surface-area, and can grow into the length that can cause phototranstormation efficiency to surpass silica-based solar cell.
Solar cell
Dye sensitization solar battery is the low-cost surrogate of traditional silicon based solar battery.Illustrate TiO among Figure 13
2The DSSC of solar cell and so on can be constructed by lower cost materials, and its price is the part of traditional silicon solar cell.Usually, DSSC comprises the crystalline nanometer particle film that is deposited on the transparent conductor.Thin film coated is in the light-sensitive coloring agent that is adhered to crystallization nanometer particle film surface.Apply layer of conductive material with ionogen, and be attached to film one side of transparent conductive material.By allowing light to pass transparent conductor and bump light-sensitive coloring agent, battery produces function.During the photon strikes dyestuff, dyestuff produces the electronics that is delivered to the crystalline membrane conduction bands.Taking place than recombination time of the electronics that produces in the faster reaction, dyestuff regains the electronics that loses from ionogen, thereby the dye molecule that prevents electronics and oxidation is compound.The electrolyte diffusion of oxidation is to negative electrode, and negative electrode replenishes electronics at this to ionogen.The electronics that is produced is transported to transparent conductor by the crystalline membrane conduction bands, leaves battery then.
Crystalline membrane often comprises the random network of nano particle, and nano particle does not provide path efficiently for electronic migration goes out film.Because collision and scattering in the nano particle random network, the electron migration that moves in film is slow, and this has produced the compound of quite a few electronics.This class solar cell also is subjected to the puzzlement a little less than the lower energy photon generation electronic capability in red and near-infrared wavelength.By the thickness of increase crystalline membrane, thereby increase the effective surface area that is exposed to photon, can produce more electronics.Yet, since electronics leave film must be through longer passage, the electronics of the increase that film thickness produced of increase is offset the electron recombination that is increased.
A kind of method of the suggestion that addresses this problem is to produce the film that comprises garden column construction rather than random network of nanoparticles.Nano wire is the more effective passage of ratio nano particle random network, can reduce the loss of electrons that causes owing to compound.Yet nano wire ratio nano particle random network has reduced surface-area (effective surface area approximately ties up 1/5) widely, thereby has significantly reduced electron production, and this has offset the benefit of improving passage.Another solution of suggestion is to produce nano-tube film.Because the extra surface-area of hollow tubular structure, described pipe ratio nano line has bigger geometrical surface, but can not grow into can with the desired thickness of light conversion efficiency of silicon-based devices competition.Therefore, requiring in the art has improved DSSC film, and this film should provide electron channel efficiently, has high surface-area, and can grow into the length that can cause phototranstormation efficiency to surpass silica-based solar cell.
In the exemplary features that the present invention uses, DSSC comprises that one deck is splashed to a titanium on the conductive glass.This glass is immersed in the acid tank that has filled moderate current, acid and oxygen in conjunction with etching metal, formation TiO
2Nano-tube array.Conductive glass and nanotube heat in oxygen, up to the nanotube crystallization and become transparent.Be coated with tubine with light-sensitive coloring agent, light-sensitive coloring agent is adhered to the surface of nanotube.Be attached to nanotube one side of conductive glass with another conductive layer of electrolytic film coating.
Embodiment 7: in another exemplary features that the present invention uses, disclose and passed through at ethylene glycol+NH
4The novel method that anodizing Ti-Fe metallic membrane is made film in the F solvent, described film are included in vertical orientated Ti-Fe-O nano-tube array on the glass substrate of the adulterated stannic oxide of fluorine (FTO) coating.TiO
2Nano-tube array is at UV illumination (100mW/cm
2) under light conversion efficiency merit attention very much, it is 16.5% under 320～400nm wavestrip illumination.Because UV-light only is a sunlight spectrographic sub-fraction, so expection has the potentiality of much higher light conversion efficiency.For example, light conversion efficiency can be potential in 18%.High light conversion efficiency partly is because TiO
2Nanotube provides transfer passage efficiently for the electronics that is produced, and this reduces widely or has eliminated and managed interior electron recombination.Described pipe can also grow into the big length that can increase effective surface area, thereby the electronics that causes increasing generates.The cost of these devices can reduce greatly from the silicon device of prior art, because material cost significantly reduces.This improved DSSC have can with the light conversion efficiency of existing silicon device competition, and production cost only is its part.These benefits have caused much lower unit source cost, make solar electric power become substitute energy feasible in many application.
Biofiltration
In another exemplary features that the present invention uses, the titania nanotube film of aperture 125nm, thickness 200 μ m shows the prospect as biofilter, as in the glucose diffusion.Biological filtering membrane typically comprises polymkeric substance, yet because its wide pore size distribution, its separation efficiency is obviously involved.TiO
2Film of Nano tube array has overcome these and other restriction of present polymer biological filtering membrane technology.
Figure 14 for example understands the device that is used for diffusion research.With cyanoacrylate adhesive described film is adhered on the aluminium sash, as shown in FIG., between two diffuser casings, seals then.With the 1mg/ml glucose solution filled chamber A of 2ml, with the pure distilled water filled chamber B of 2ml.The device of assembling rotates with 4rpm in whole experiment all the time, to eliminate any effect of boundary layer.Every 30 minutes from chamber B collected specimens, reach 3 hours.(Glucose GO Sigma) and by spectrophotometric colorimetric reading measures concentration with quantitative method of analyzing enzyme.The concentration of measuring (C) is drawn with respect to the time variation with the ratio of original concentration (Co), to determine the diffusion transport by film.
Crossing over the glucose diffusion processes of the film of good chamber A of two stirrings of separation and B can describe with first diffusion law of Fick:
Wherein J is a mass flux, D
EffBe effective diffusion coefficient, A
EffBe the section hole area, L is a film thickness, C
AAnd C
BCorrespondingly be the measurement concentration of chamber A (giving body) and B (acceptor).Can regard flux as steady state, because chamber A regards as the unlimited source of glucose in experimentation, its change in concentration is ignored.Figure 15 has shown the measurement concentration with respect to time B one side; Have the linear relationship of height, it shows it is zeroth order diffusion system or zeroth order release profiles.
With this equation and mass balance equation coupling, can use following formula to calculate spread coefficient:
C wherein
A0Be the starting point concentration among the A of chamber, C
BBe the measurement concentration among the B of chamber, Δ L is a film thickness, and V is the cumulative volume of chamber A and B, and t is the time.According to the Stokes-Einstein Equation for Calculating, the spread coefficient in the water removes D then
Eff, spread coefficient is carried out normalization method:
Wherein k is a boltzmann constant, and T is a temperature, and η is a solvent viscosity, R
dBe the Stokes radius.We find that glucose passes the effective diffusion coefficient D of described film (thick 200 μ m, aperture 125nm)
Eff=1.28x10
-6, the D of water
H2O=6.14x10
-6, its ratio D
Eff/ D
H2O=0.2.
The preferred embodiments of the invention are illustrated in drawing and description, although used specific term, it uses a meaning for general remark, and are not used in the purpose of qualification.Requirement according to circumstances or for facility only otherwise deviate from spirit of the present invention and the protection domain that following claim institute further limits, can be considered the change of parts formation ratio and the change that is equal to replacement.
Reference:
All reference that this specification sheets is listed from start to finish comprise and list in following reference, at this its full content are combined in this by reference.
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Claims (28)
1. method of using electrochemical oxidation to form vertical orientated Nano tube array of titanium dioxide, this method comprises:
Two electrodes with working electrode and counter electrode structure is provided; And
The described working electrode of anodizing in ionogen, described ionogen has been optimized between process of growth and dissolution process and has kept running balance, with by lasting chemical oxidation that working electrode is provided and the dissolved hole growth of passing through the oxide compound that formed, promote the growth of nano-tube array.
2. the process of claim 1 wherein that described ionogen is ethylene glycol or polarity organic electrolyte, this polarity organic electrolyte comprises methane amide, methyl-sulphoxide, dimethyl formamide or the N-methylformamide that is used to provide fluoride ion.
3. the process of claim 1 wherein that described working electrode is a titanium foil, its thickness is enough to provide length to surpass the synthesizing from the directed nano-tube array of closely assembling of 10 μ m.
4. the process of claim 1 wherein that described working electrode is a titanium foil, its thickness is enough to provide length to have the synthesizing from the directed nano-tube array of closely assembling of 134 μ m at least.
5. the process of claim 1 wherein that described working electrode is a titanium foil, its thickness is enough to provide length to surpass the synthesizing from the directed nano-tube array of closely assembling of 1000 μ m.
6. the method for claim 5, the thickness of wherein said titanium foil is 2.0mm at least.
7. the method for claim 3, the thickness of wherein said titanium foil is 0.25～2.0mm.
8. the process of claim 1 wherein described ionogen be the aqueous solution, based on the ionogen or the nonaqueous electrolyte of acid amides.
9. the process of claim 1 wherein that described ionogen is the NH that contains 0.3wt%
4F and 2% H
2The ethylene glycol of O.
10. the process of claim 1 wherein that described ionogen is the DMSO organic electrolyte that contains following fluorochemical: hydrofluoric acid, Potassium monofluoride or Neutral ammonium fluoride.
11. the method for claim 10, it also comprises the electrolysis composition and the step of oxidation time length of the organic electrolyte of optimizing fluoride, so that the complete anodizing of working electrode to be provided, and to the control of nano-tube array length.
12. the method for claim 1, it also comprises the following steps that promote that nano-tube array length increases: the NH that contains 0.5wt% in ethylene glycol
4F and 3.0% H
2Anodizing working electrode in the ionogen of O.
13. the process of claim 1 wherein that described counter electrode comprises platinum foil.
14. a method of using electrochemical oxidation to form vertical orientated nano-tube array, this method comprises:
Two electrodes with working electrode and counter electrode structure is provided; And
The described working electrode of anodizing in ionogen provides the oxide compound of formation;
Dissolve the oxide compound of this formation, to form nano-tube array;
By controlling one or more anodizing variablees, keep the running balance between process of growth and the dissolution process; And
By the lasting oxidation of working electrode, make described nano-tube array grow to the total length that forms nano-tube array.
15. the method for claim 14, wherein said ionogen is for providing the polarity organic electrolyte of fluoride ion, and described polarity organic electrolyte is selected from following group:
A) methane amide (FA);
B) methyl-sulphoxide (DMSO);
C) dimethyl formamide (DMF); With
D) N-methylformamide (NMF).
16. the method for claim 14, wherein said polarity organic electrolyte is selected from following group:
A) hydrofluoric acid (HF);
B) Potassium monofluoride (KF); With
C) Neutral ammonium fluoride (NH
4F).
17. the method for claim 14, wherein said working electrode comprises titanium foil.
18. the method for claim 17, wherein said counter electrode comprises platinum foil.
19. the method for claim 18, wherein formed oxide compound comprises titanium oxide.
20. the method for claim 19, wherein said ionogen comprises ethylene glycol solution, and described ethylene glycol helps to reduce to the lateral etch of nanotube minimum.
21. the method for claim 20, it also comprises by optimizing the NH of the weight percentage that is comprised in the ethylene glycol solution
4F and H
2The ionogen of O, the certain thickness titanium foil of anodizing fully.
22. the method for claim 21, wherein said anodized variable comprises at least:
A) anodizing voltage;
B) the anodizing time;
C) H in the ethylene glycol solution
2The weight percentage of O; With
D) NH
4The weight percentage of F.
23. the method for claim 22, it also comprises makes nano-tube array obtain the following steps that total length is at least 1000 μ m: the titanium foil that has adequate thickness by use, and under enough big anodizing voltage and time, the NH of contained weight percentage in ethylene glycol solution
4F and H
2The described titanium foil of anodizing in the ionogen of O.
24. a method of using electrochemical oxidation to form nano-tube array, this method comprises:
Provide with titanium foil as working electrode with the two electrodes structure of platinum foil as counter electrode;
The anodizing titanium foil forms titanium dioxide in electrolyte solution, and described electrolyte solution comprises the NH of certainweight percentage ratio
4F and H
2O is in ethylene glycol solution;
Dissolve described titanium dioxide, show the nano-tube array of the long-range order of tight assembling and high aspect ratio with formation;
Titanium foil oxidation and hole growth by continuing make nano-tube array grow to the optimum length of gained working electrode thickness; And
By controlling the running balance between following variable maintenance process of growth and the dissolution process:
A) anodizing voltage;
B) the anodizing time; With
C) NH in the ethylene glycol solution
4F and H
2The weight percentage of O.
25. the method for claim 24, it also comprises the following steps that the nano-tube array of at least 1000 μ m length is provided by the thick titanium foil of 0.5mm: under the anodizing time of the anodizing voltage of 60V and 216 hours, contain the NH of 0.5wt% in ethylene glycol solution
4F and 3.0% H
2The thick titanium foil of this 0.5mm of anodizing in the ionogen of O.
26. a nano-tube array, it comprises:
A plurality of self-orientating vertical orientated length are the titania nanotube of at least 10 μ m;
Wherein a plurality of certainly directed vertical orientated titania nanotubes form by electrochemical oxidation.
27. a solar cell, it comprises:
Solar cell surface;
Be pasted to the nano-tube array on described surface, described nano-tube array comprises a plurality of from the titania nanotube of directed vertical orientated length at least 10 μ m;
Wherein said Nano tube array of titanium dioxide is formed by electrochemical oxidation.
28. a biofilter, it comprises:
The biofilter surface;
Be pasted to the nano-tube array on described surface, described nano-tube array comprises a plurality of from the titania nanotube of directed vertical orientated length at least 10 μ m;
Wherein said Nano tube array of titanium dioxide is formed by electrochemical oxidation.
Applications Claiming Priority (3)
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|---|---|---|---|
| US95211607P | 2007-07-26 | 2007-07-26 | |
| US60/952,116 | 2007-07-26 | ||
| PCT/US2008/071166 WO2009015329A2 (en) | 2007-07-26 | 2008-07-25 | Highly-ordered titania nanotube arrays |
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ID=40282160
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| US (1) | US20100187172A1 (en) |
| EP (1) | EP2191040A2 (en) |
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| WO (1) | WO2009015329A2 (en) |
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| CN103774169A (en) * | 2014-01-20 | 2014-05-07 | 西安理工大学 | Preparation method of TiO2 nanotube with scattered through holes |
| CN103774169B (en) * | 2014-01-20 | 2016-08-17 | 西安理工大学 | A kind of TiO disperseing through hole2the preparation method of nanotube |
| CN106456310A (en) * | 2014-06-24 | 2017-02-22 | 加利福尼亚大学董事会 | Nickel titanium oxide coated articles |
| CN105588864A (en) * | 2015-12-18 | 2016-05-18 | 清华大学深圳研究生院 | Electrode, preparation method thereof, and electrochemical biosensor |
| CN105588864B (en) * | 2015-12-18 | 2019-01-29 | 清华大学深圳研究生院 | A kind of electrode and preparation method thereof and electrochemica biological sensor |
| CN107068408A (en) * | 2017-04-18 | 2017-08-18 | 河西学院 | It is a kind of for light anode of DSSC and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| WO2009015329A2 (en) | 2009-01-29 |
| EP2191040A2 (en) | 2010-06-02 |
| US20100187172A1 (en) | 2010-07-29 |
| WO2009015329A3 (en) | 2009-04-16 |
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